QTAIM-Based Local Potential Energy Model: Applications and Limitations to Quantify the Binding Energy of Intra/intermolecular Interactions

In previous work, we developed the local potential energy model, LPE, based on the electrostatic force and QTAIM topological data to quantify classical hydrogen bond energies. In this work, we extended the investigation to other inter/intramolecular interactions (non-conventional hydrogen bonds and others). The LPE presented high precision and linearity with supramolecular binding energy, when excluding interactions of an ion with π-bonded groups or polar molecule. The energy decomposition analysis from SAPT-DFT and LMOEDA showed that dispersion and electrostatic components are important to LPE, while polarization component impairs it. The LPE cannot be used for complexes with predominant polarization component.